Structural studies on ruthenium carbonyl hydrides. 13. Synthesis of

0t-H)3Ru3(M3-CSEt) (CO)9 is synthesizedby treatment of (/i-H)3Ru3(g3-CBr) (CO)9 with ethanethiol and triethylamine and has been fully characterized by...
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Organometallics 1987, 6 , 806-812

Synthesis of (p-H),Ru,(p3-CSEt) (CO), and Its Rearrangement to (p-H)Ru3(p,-q2-CH2SEt) (CO),. Crystal Structure of (p-H)Ru3(p3-q2-CH2SEt)(CO),' Melvyn Rowen Churchill," Joseph W. Ziller, Dennis M. Dalton, and Jerome

B. Keister*

Department of Chemistry, University at Buffalo, State University of New York, Buffalo, New York 14214 Received October 6, 1986

(~-H),RU,(~,-CSE~)(CO)~ is synthesized by treatment of (p-H)3R~3(p3-CBr)(C0)9 with ethanethiol and triethylamine and has been fully characterized by spectroscopic methods. Upon heating at 50-60 "C, (F-H),RU,(~~-CSE~)(CO)~ rearranges to ( ~ - H ) R u ~ ( ~ ~ - ~ ~ - C(46% H ~ Syield), E ~ ) characterized (C~)~ by spectroscopy and by X-ray CrystaJlography. (~-H)RU~(~~-~~-CH,SE~)(CO)~ crystallizes in the centrosymmetric monoclinic space group P 2 , / n (No. 14) with a = 8.2639 (10) A, b = 16.8680 (17) A, c = 13.7886 (15) A, fl = 93.788 (9)", V = 1917.9 (4) A3, and 2 = 4. X-ray diffraction data (Mo Ka, 28 = 4.5-45.0') were collected with a Syntex P21 automated four-circle diffractometer, and the structure was refined to RF = 6.0% for all 2523 unique reflections (RF= 2.9% for those 1732 reflectionswith lFol > 6a((F,I)). The complex contains a triangular cluster of ruthenium atoms, each of which is linked to three terminal carbonyl ligands. The ~,-TJ~-CH,SE~ ligand caps the triruthenium cluster with the sulfur atom bridging Ru(2) and Ru(3) [Ru(2)-S = 2.348 (2) A, Ru(3)-S = 2.302 (2) A, and Ru(2)-S-Ru(3) = 73.07 (7)O]and with the methylene carbon atom, C(1), bonded to Ru(1) [Ru(l)-C(l) = 2.188 (9) A]. A hydride ligand bridges the Ru(1)-Ru(2) edge in the equatorial plane, with Ru(l)-H(12) = 1.61 ( 7 ) ,Ru(2)-H(12) = 1.87 (7) A, and Ru(l)-H(12)-Ru(2) = 117 (4)'. The Ru-Ru bond distances are inequivalent [Ru(l)-Ru(2) = 2.974 (l),Ru(l)-Ru(3) = 2.818 (l), and Ru(2)-Ru(3) = 2.769 (1) A], with the edge bridged by the hydride ligand having the longest distance. The rearrangement of (p-H),Ru3(p3-CSEt)(C0),to (~~-H)RU~GL~-~~-CH&~E~)(CO)~ involves two C-H reductive eliminations, the two unsaturated metal atoms thus formed being stabilized by coordination of the sulfur atom. Thus, GL-H)Ru3GL3-q2-CH~Et)(C0)g is a stabilized alkyl analogous to an intermediate in the previously reported "desorption" of CH3X from (cL-H)~Ru,(F~-CX)(CO), (X = Ph, C1, or C02Me)forming RU~(CO)~, under a CO atmosphere. The chemistry of the (~-H),RU,(~,-CX)(CO)~ cluster series has proved to be a important entry into a basic understanding of fundamental processes occurring on polymetallic units. The mechanisms of ligand substitution,la reductive elimination of molecular hydrogen,2hydrogen transfer to unsaturated hydrocarbon^,^ and insertion of alkynes into the Ru-C bond4have been investigated in our laboratory. The structure^,^ bonding,6 and spectroscopic properties7 of these clusters have also been the subjects of recent studies. The nature of the methylidyne substituent frequently has a major role in determining the chemistry of the cluster. For example, in reactions of (1) This paper constitutes part 13 of the series "Structural Studies on Ruthenium Carbonyl Hydrides". Recent previous parts include the following. (a) Part 7: Abdul Rahman, 2.;Beanan, L. R.; Bavaro, L. M.; Modi, S. P.; Keister, J. B.; Churchill, M. R. J. Organomet. Chem. 1984, 263, 75. (b) Part 8 Churchill, M. R.; Fettinger, J. C.; Keister, J. B. Organometallics 1985,4,1867.(c) Part 9 Churchill, M. R.; Fettinger, J. C.; Keister, J. B.; See, R. F.; Ziller, J. W. Organometallics 1985,4,2112. (d) Part 1 0 Churchill, M. R.; Ziller, J. W.; Keister, J. B. J. Organomet. Chem. 1985,297, 93. (e) Part 11: Churchill, M. R.; Duggan, T. P.; Keister, J. B.; Ziller, J. W. Acta Crystallogr., Sect. C: Cryst. Struct. Commun., accepted for publication. (0Part 12 Churchill, M. R.; Janik, T. S.; Duggan, T. P.; Keister, J. B. Organometallics, preceding paper in this issue. (2)(a) Bavaro, L.M.; Montangero, P.; Keister, 3. B. J.Am. Chem. SOC. 1983,105,4977.(b) Bavaro, L. M.; Keister, J. B. J. Organornet. Chem. 1985,287,357. (c) Dalton, D. M.; Barnett, D. J.; Duggan, T. P.; Keister, J. B.; Malik, P. T.; Modi, S. P.; Shaffer, M. R.; Smesko, S. A. Organometallics 1985,4, 1854. (3)Churchill, M. R.; Beanan, L. R.; Wasserman, H. J.; Bueno, C.; Abdul Rahman, 2.; Keister, J. B. Organometallics 1983,2,1179. (4)Beanan, L. R.; Keister, J. B. Organometallics 1985,4, 1713. (5)(a) Zhu, N. J.; Lecomte, C.; Coppens, P.; Keister, J. B. Acta Crystallogr., Sect. B Struct. Crystallogr. Cryst. Chem. 1982,B38,1286. (b) Sheldrick, G. M.; Yesinowski,J. P. J . Chem. Soc., Dalton Trans. 1975, 873. (d) Castiglioni, M.; Gervasio, G.; Sappa, E. Inorg. Chim. Acta 1981, 49, 217. (6)Sherwood, D. E.,Jr.; Hall, M. B. Organometallics 1982,I , 1519. (7)(a) Oxton, I. A. Spectrochim. Acta, Part A 1982,38A, 181. (b) Evans, J.;McNulty, G. S. J . Chem. SOC.,Dalton Trans. 1984,79.

(pH)3R~3(p3-CX)(C0)9 with CO, reductive elimination of hydrogen occurs when X is OMe2but reductive elimination of CHBXproceeds when X is C02Me, C1, Ph, and others.8 To further investigate the influence of the substituent upon the reactivity of these clusters, we have prepared the new cluster (p-H)3R~3(p3-CSEt)(C0)9 and report here its thermally induced rearrangement to (p-H)Ru3(p3q2CH,SEt)(CO),, fully characterized by X-ray crystallogra~ h y This . ~ rearrangement involves reductive elimination of two C-H bonds, the first two in the sequence leading to alkane from (c~-H)~Ru~(~,-CX)(CO)~ Elsewhere we have reported that a single C-H reductive elimination occurs upon pyrolysis of (p-H),Ru3(p3-CC02Me)(CO),,forming the stabilized alkylidene (p-H)2R~3(p3-~2-CHC(0)OMe)(CO),, also characterized by X-ray crystallography.lf

Experimental Section General Data. (p-H)3R~3(w3-CBr)(C0)9 was prepared by a previously published procedure.10 Infrared spectra were recorded on a Beckman 4250 spectrophotometer as cyclohexane solutions and were referenced to the 2138.5 cm-' absorption due to cyclohexane. 'H and I3C NMR spectra were recorded on a JEOL FX-9OQ spectrometer; Cr(acac), (0.02 M) was added as a relaxation agent for the 13C spectra. Mass spectra were recorded at the Penn State University Mass Spectrometry Center by Dr. R. Minard. Elemental analyses were obtained from Schwarzkopf Microanalytical Laboratories. (c(-H)~Ru~(~~-CSE~)(CO)~ Ethanethiol (46 fiL, 0.63 mmol) and triethylamine (52 kL, 0.38 mmol) were added to a solution of (fi-H),R~,(fi~-CBr)(C0)~ (81.6 mg, 0.125 mmol) in 5 mL of dry cyclohexane. T h e mixture was stirred under nitrogen at room (8) Duggan, T. P.; Barnett, D. J.; Muscatella, M. J.; Keister, J. B. J. A m . Chem. Soc. 1986,108, 6076. (9)A preliminary report of the syntheses and spectroscopic characterizations has appeared Dalton, D. M.; Keister, J. B. J . Organornet. Chem. 1985,290,C37. (10)Keister, J. B.; Horling, T. L. Inorg. Chern. 1980,19, 2304.

0276-733318712306-0806$01.50/0 0 1987 American Chemical Society

Organometallics, Vol. 6, No. 4, 1987 807

S t r u c t u r e of (p-iY)Ru3(p3-?lz-CHzSEt) (CO)9 Table I. Experimental Data for t h e X-ray Diffraction Study of ( ~ - H ) R u ~ ( ~ ~ - $ - C H $ ~ E ~ ) ( C O ) S (A) Crystallographic Parameters a t 20 "C (293 K) cryst system: monoclinic formula: C12HB09R~3S mol w t 631.5 space group: P 2 ' / n (No. 14) z = 4 Q = 8.2639 (10) 8, D(ca1cd) = 2.19 g cm-, b = 16.8680 (17) A c = 13.7886 (15) 8, p(Mo Ka) = 24.2 cm-I = 93.788 (9)" V = 1917.9 (4) A3 (B) Collection of X-ray Diffraction Data diffractometer: Syntex P2, radiation: Mo Ka = 0.710730 A) monochromator: highly oriented (pyrolytic) graphite, 28(m) = 12.160" for 002 reflection, equatorial mode, assumed to be 50% perfect/50% ideally mosaic for polarization correction reflctions measd: +h,+k,hl for 28 = 4.5-45.0'; 2726 reflections measured and merged to 2523 unique data; no datum rejected scan type: coupled B(crystal)-28(counter) scan width: [28(Mo Ka,) - 0.91 [28(Mo Ka2) + 0.91" scan speed: 4.0 deg min-' background measurement: stationary crystal and stationary counter at each end of the 28 scan; each for one-half of total scan time

(x

-

Table 11. Final Positional Parameters for atom

X

(~L-H)Ru~(~~-~~-CH~SE~)(CO)~ Y Z Baa... A2

0.18730 (8) 0.25802 (8) 0.484 29 (8) 0.425 84 (26) 0.3107 (12) 0.571 5 (15) 0.689 1 (15) 0.337 44 (85) 0.03095 (94) -0.10282 (85) 0.497 0 (10) 0.0126 (11) 0.11808 (85) 0.676 60 (82) 0.77253 (92) 0.38045 (89) 0.282 5 (10) 0.0898 (11) -0.0015 (11) 0.408 4 (12) 0.1036 (12) 0.1690 (11) 0.6025 (11) 0.6630 (12) 0.421 2 (11) 0.1150 (88) 0.402 (12) 0.231 5 (91) 0.514 (10) 0.635 (11) 0.755 9 0.737 0 0.615 1

0.37894 (4) 0.14059 (5) 0.354 78 (5) 0.38476 (4) 0.433 75 (4) 0.22801 (5) 0.304 27 (12) 0.26534 (16) 0.26553 (48) 0.16751 (68) 0.232 87 (68) 0.32087 (84) 0.206 13 (82) 0.247 60 (87) 0.386 73 (37) -0.054 60 (48) 0.542 75 (41) 0.11992 (55) 0.28232 (44) 0.05783 (55) 0.402 29 (45) 0.53078 (55) 0.28254 (51) 0.45571 (59) 0.54987 (42) 0.383 29 (56) 0.429 64 (40) 0.04702 (53) 0.46758 (55) 0.371 53 (65) 0.60583 (37) 0.20954 (56) 0.385 32 (46) 0.02038 (66) 0.48255 (56) 0.128 19 (63) 0.31881 (53) 0.09243 (66) 0.396 77 (52) 0.46431 (72) 0.31992 (59) 0.41971 (69) 0.48833 (58) 0.37297 (64) 0.43069 (50) 0.11445 (73) 0.45441 (63) 0.31746 (80) 0.541 19 (55) 0.21652 (65) 0.3695 (37) 0.2457 (53) 4.8 (18) 0.1033 (76) 9.9 (30) 0.2424 (58) 0.2247 (45) 0.1873 (55) 4.9 (20) 0.3447 (65) 6.4 (24) 0.1853 (55) 0.269 1 (55) 0.3687 (70) 7.3 (29) 0.164 7 6.0 0.271 0 0.244 9 6.0 0.216 4 0.1766 6.0 0.192 2

temperature for 8 h. Evaporation of the solvent and purification by preparative TLC (silica gel, cyclohexane/dichloromethane,51) yielded (~~-H),RU~(~~-CSE~)(CO)~ as an orange powder (40.2 mg, 0.064 mmol, 51 %). In a typical reaction, the 5:3:1 molar ratio of HSEt:Et,N(p-H)3R~3(p3-CBr)(C0)9 resulted in yields ranging from 40 t o 60%. Increased reaction times caused excessive decomposition of the cluster as did use of dichloromethane as the solvent. ( ~ - H ) , R U ~ ( ~ ~ - C S E ~was ) ( Ccrystallized O)~ from methanol as dark orange crystals. Anal. Calcd for C12H809Ru3S: C, 22.82; H, 1.28. Found: C, 22.82; H, 1.57. IR (CcHiz): u(CO) 2107 VW, 2080 VS, 2036 VS, 2029 to unscaled IFo\values, and were placed on an approximate abm, 2019 s, 2007 vw cm-'. 'H NMR (CDC13, 25 "C): 3.18 ( q , 2 H, solute scale by means of a Wilson plot. Any reflection with Z(net) CHz), 1.40 (t, 3 H, CH,), -17.55 (s, 3 H, RuHRu) ppm. l3C{'H) < 0 was assigned the value lFol = 0. No datum was rejected. NMR (CDCI,, 22 "C): 204.4 (1 C, methylidyne carbon), 189.5 (3 Solution a n d Refinement of the Structure. All calculations C, axial CO), 189.4 (6 C, equatorial CO), 43.3 (1 C, SCH2Me), 12.9 were performed on our locally modified version of the Syntex XTL (1 C, CH,) ppm. E1 MS: m / z 634 (102R~3). ( ~ - H ) R u ~ ( ~ ~ - $ - C H ~ S E ~ )((~C- O H ) *~ R u ~ ( ~ B C S E ~(110 ) ( C O ) ~ system. The analytical form of the appropriate neutral atom scattering factor was corrected for both the real ( A f ' ) and mg, 0.174 mmol) was dissolved in 20 mL of dry cyclohexane under imaginary (i Af ") components of anomalous dispersion.12 The nitrogen. The mixture was heated a t 55-60 "C for 51 h, resulting function minimized during least-squares refinement was Cw(IFo[ in a dark orange-brown solution. Following evaporation of the - IFCJ)', where w = [(UJF~I)~ + (0.015~F01)21-'. solvent, the residue was dissolved in dichloromethane and purified The structure was solved by using direct methods (MULby preparative TLC (silica gel, cyclohexane/dichloromethane,5:l) TAN).', The positions of the three ruthenium atoms were deyielding crude orange-yellow crystals of (p-H)Ru,(g3-+termined from an E map. All remaining atoms (other than the CHzSEt)(CO)g(51 mg, 0.081 mmol, 46%). Recrystallization from hydrogen atoms of the methyl group centered on C(3)) were methanol provided well-formed yellow crystals suitable for X-ray located from a series of difference Fourier syntheses. Hydrogen analysis. atoms of the methyl group were included in calculated positions Anal. Calcd for ClzH809Ru3S: C, 22.82; H, 1.28. Found: C, with d(C-H) = 0.95 and were included in a staggered con22.85; H, 1.14. IR (C6H12): v(C0) 2089 m, 2060 s, 2036 vs, 2017 formation. Refinement of positional and anisotropic thermal s, 2005 m, 2000 m cm-'. 'H NMR (CDCI,, 22 "C): 2.47 ( q , 2 Ha, parameters for all non-hydrogen atoms and positional and iso-SCH2Me), 1.37 (d, 2 Hb, -CHzSEt), 1.13 (t, 3 H,, CH,), -16.58 tropic parameters for the hydride ligand and hydrogen atoms of (t, 1 Hd, RuHRu) ppm, J,, = 7.3 Hz, J,,,,= 1.5Hz. 13C{1H)NMR the methylene groups led to convergence with15 RF = 6.0%, RwF (CDCl,, 23 "C): 196.7 (1 C), 194.0 (br, 8 C), 54.5 (1 C, SCH,Me), = 3.9%, and GOF = 1.17 for 246 variables refined against all 2523 11.4 (1 C, CH,), -9.9 (1 C, CH2SEt) ppm. E1 MS: m / z 634 reflections. (Data/parameter ratio = 10.3:l.) Residuals for those (lo2Ru3). 2019 reflections with 1F.J > 3u(1Po,1)were RF = 3.9%, R w =~3.5% Collection of X-ray Diffraction D a t a f o r (p-H)Ru,!p3and for those 1732 reflections with IFoI > 6u(lFoI)were RF = 2.9% q2-CHzSEt)(CO)9. A yellow crystal of approximate dimensions and RwF = 3.0%. An isotropic correction for secondary extinction 0.10 X 0.13 X 0.20 111111, was sealed in a glass capillary under a was applied. nitrogen atmosphere and accurately aligned on our Syntex P21 Analysis of the function Zw(lFol - lFc1)2showed no unusual automated diffractometer. Subsequent set-up operations (detrends as a function of Miller indices, magnitude of IFol, (sin @/A, termination of accurate cell dimensions and orientation matrix) or sequence number. A final difference Fourier synthesis was and collection of the intensity data were carried out by the essentially featureless. The structure is thus both correct and previously described techniques of this laboratory;'' details appear in Table I. The systematic absences h01 for h + 1 = 2n + 1 and OkO for k = 2n + 1 uniquely define the centrosymmetric mono(12) International Tables for X - R a y Crystallography; Kynoch Birclinic space group R 1 / n . mingham, England, 1974; Vol. 4: (a) pp 99-101; (b) pp 149-150. All data were corrected for the effects of absorption ( p = 24.2 (13) Germain, G.; Main, P.; Woolfson, M. M. Acta CJy.9tdOgr., Sect. cm-') and for Lorentz and polarization effects, were converted A: Cryst. Phys., Diffr., Theor. Gen. Crystallogr. 1971, A27, 368. (14) Churchill, M. R. Inora. Chem. 1973. 12. 1213. (11) Churchill, M. R.; Lashewycz, R. A.; Rotella, F.J. Znorg. Chem.

1977, 16, 265.

808 Organometallics, Vol. 6, No. 4, 1987

Churchill et al.

complete. Final atomic positions are collected in Table 11. Anisotropic thermal parameters appear as supplementary material.

Results Synthesis of (p-H),R~~(fi~-CsEt)(Co)~ Our synthesis of (p-H)3Ru3(p3-CSEt)(C0)9 was developed by analogy to the base-catalyzed displacement of halide used to prepare (~-H),RU~(~~-COE~)(CO);~ and CO,(~~-CSR)(CO)~'~ Best yields were obtained from reactions of (p-H),Ru3(p3CBr)(C0)9 with 5 equiv of ethanethiol and 3 equiv of triethylamine in cyclohexane solution and by allowing the reaction to proceed only until the IR spectrum indicated that no starting material remained. No reaction under these conditions occurred in the absence of triethylamine. Poorer yields were obtained in more polar solvents such as dichloromethane, acetonitrile, or THF. With a large Figure 1. Labeling of atoms in the GL-H)RU,(~~-~~-CH,SE~)(CO)~ excess of ethanethiol extensive decomposition resulted. molecule [ORTEP-11 diagram; 30% probability ellipsoids for all Low yields were also obtained by using NaSEt/ethanethiol non-hydrogen atoms; hydrogen atoms artificially reduced). (@lo%), LiSEt/ethanethiol (0-lo%), NaHCO,/ethanethiol (0-10 % ), ethanethiol/dichloromethane (10% ), composition of the product was readily apparent from the MezSn(SEt)2/dichloromethane (0-5%),26 or ethanethiol spectroscopic data, the connectivity, particularly of the SEt alone (0-10%). and methylene groups, could not be established without The new cluster ( ~ - H ) , R U ~ ( ~ , - C S E ~ )is( C aO red-or)~ recourse to X-ray crystallography. The E1 mass spectrum ange crystalline solid, air-stable and soluble in common is very similar to that of (~-H),RU,(~,-CSE~)(CO)~, disorganic solvents. The E1 mass spectrum displays the playing the molecular ion and ions derived by sequential molecular ion and ions resulting from stepwise loss of the loss of CO. The IR spectrum contains only terminal CO CO ligands; satisfactory elemental analyses were obtained. stretches. The 'H NMR spectrum at room temperature The IR spectrum contains absorptions due to terminal CO consists of resonances at -16.58 (t, 1 H, RuHRu) and 1.37 stretching modes in a rather simple pattern characteristic (d, 2 H, CH,SEt) ppm coupled to one another with a of molecules of this cla~s.'~'~ The 'H NMR spectrum coupling constant of 1.5 Hz, in addition to resonances due consists of a singlet at -17.55 ppm due to three equivalent to the SEt group (2.47 (q,2 H, SCH,Me) and 1.13 (t,3 H, bridging hydride ligands and resonances due to the Et CH,) ppm, J = 7.3 Hz). Although the protons of both group (3.18 (2 H, q) and 1.40 (3 H, t) ppm, J = 7.2 Hz). methylene groups are diastereotopic, only single resonances The 13CNMR spectrum consists of a resonances at 204.4 are seen for each set at room temperature. (1C) ppm, assigned to the methylidyne carbon, 189.5 (3 Both 'H and 13CNMR spectra show evidence for fluxC) ppm, assigned to the axial carbonyls, 189.4 (6 C) ppm, ional processes. A t -60 "C the static proton spectrum assigned to the equatorial carbonyls, 43.3 (1C) ppm, asdisplays nonequivalent methylene reasonances for the SEt signed to the methylene carbon, and 12.9 (1 C) ppm, asgroup; although the other methylene protons are also signed to the methyl carbon. diastereotopic, there is apparently an insignificant difSynthesis of ( ~ - H ) R u ~ ( ~ ~ - . ~ ~ ~ - C H ~The SE~)(C O ) ~ between the chemical shifts of these two since only ference nature of the methylidyne substituent X is an important a broad singlet is observed. An estimate of the free energy factor that determines the path of the reaction of (Fof activation, 51 (A2) kJ/mol(l2.2 (*0.5) kcal/mol), was H)3R~3(p3-CX) (CO), with CO. We had previously noted determined from the apparent coalescence temperature that strong n-donating substituents,such as OMe or NMe2, of -35 "C for the two quartets of the SEt protons.17 A facilitate reductive elimination of hydrogen, forming (pmechanism that would account for the observed spectra H)RU~(~-CX)(CO)~~: whereas for other substituents, such is exchange of the hydride between the two Ru-Ru edges as Ph, C1, or CO,Me, the most facile pathway is reductive not bridged by S; this would generate an apparent plane elimination of CH3X.8 Since the SEt group should be a of symmetry bisecting the methylene protons. Such poorer a-donor than OMe but a better one than Ph or C1, fluxional processes are commonly observed for ( F both reaction paths were possibilities. Unexpectedly, (FH),M,(p3-rl2-L)(CO),clusters.18 Indeed, we have reported H),Ru3(p3-CSEt)(CO),,even in the presence of CO (1atm), a closely related exchange process for (p-H)2R~3(p3-$= rearranges to ( ~ - H ) R U ~ ( ~ ~ - ~ ~ - C H (Figure ~ S E ~l), ) ( C OCHC(O)OCH,)(CO), )~ having AG* C 54 kJ/mol (13 kcal/ characterized by spectroscopic methods and by X-ray mol). crystallography. The I3C NMR spectrum at 23 "C also exhibits fluxional A t 70.6 "C the rate constant for the rearrangement of behavior. Only two signals, a sharp peak at 196.7 ppm and (~L-H),Ru~(~,-CSE~)(CO)~ to (pu-H)Ru,G,-r12-CH2SEt)(C0)g a very broad one at 194.0 pprn with relative areas of 123, in decahydronaphthalene solution and under a nitrogen appear in the carbonyl region; we did not attempt to obtain atmosphere is 2.2 X lo4 s-l, correspondingto a free energy the static spectrum. We presume that the sharp signal is of activation of 25.9 kcal/mol. However, the rate is dedue to the unique CO ligand trans to the alkyl carbon. pendent upon the solvent, apparently increasing with inSome process or processes involving CO migration, in adcreasing solvent polarity. At 25 "C in acetone solution the dition to hydride migration, are required to average the rearrangement is ca. 50% complete after 60 h. A complete other eight resonances. The CH2SEt resonance occurs at kinetic study of the reaction is in progress, and the results will be published in a later paper. (17)At -59 "C the separation between the two quartets is 6.8 Hz.Our (~-H)RU~(~,-~~-CH,SE~)(CO)~ is a yellow crystalline solid best estimate of the coalescence temperature is -35 "C. At coalescence: k , = 2%Au, where Au is the separation in hertz in the absence of exthat is soluble in common organic solvents. Although the (16) Seyferth, D.; Rudie, C. N.; Merola, J. S. J. Organomet. Chem. 1978, 144, C26.

change: Wilkins, R. G. T h e S t u d y of Kinetics and Mechanism of Reactions of Transition Metal Complexes; Allyn and Bacon: Boston, 1974; p 154. (18) For examples see ref If and other references therein.

Structure of

Organometallics, Vol. 6, No. 4, 1987 809

Figure 2. Stereoscopic view of the ( ~ - H ) R U ~ ( ~ ~ - ~ ~ - C H molecule. ~SE~)(CO)~ Table 111. Interatomic Distances (A) for ( ~ L - H ) R U ~ ( ~ ~ - ~ ' -(COh CH~SE~) (A) Ru-Ru, Ru(l)-Ru(2) Ru(l)-Ru(3) Ru(2)-Ru(3) Ru(l)-H(12) Ru(l)-C(ll) Ru(l)-C(12) R~(l)-C(13) Ru(2)-C(21) Ru(2)-C(22) Ru(2)-C(23) Ru(3)-C(31) Ru(3)-C(32) Ru(3)-C(33)

Ru-CHzSEt, 2.974 (1) 2.818 (1) 2.769 (1) 1.61 (7)

(B) Ru-CO and 1.884 (9) 1.927 (9) 1.941 (9) 1.902 (10) 1.944 (10) 1.918 (10) 1.900 (10) 1.893 (10) 1.890 (9)

and Ru-(pH) Distances Ru(2)-S 2.348 (2) Ru(3)-S 2.302 (2) Ru(l)-C(l) 2.188 (9) R~(2)-H(12) 1.87 (7) C-0 Distances C(ll)-O(ll) C(12)-0(12) C(13)-O(13) C(21)-0(21) C(22)-0(22) C(23)-0(23) C(31)-0(31) C(32)-0(32) C(33)-0(33)

1.157 (11) 1.129 (12) 1.120 (12) 1.138 (13) 1.122 (13) 1.133 (12) 1.147 (12) 1.156 (13) 1.143 (11)

(A) Angles within the Ru3(r3-q2-CHzSEt) System R u ( ~ ) - R u ( I ) - R u ( ~ ) 57.04 (2) Ru(Z)-Ru(l)-C(l) 78.55 (24) R u ( ~ ) - R u ( ~ ) - R u ( ~ )58.64 (2) Ru(3)-Ru(l)-C(1) 80.28 (24) R u ( ~ ) - R u ( ~ ) - R u ( ~ )64.32 (2) Ru(2)-S-C(1) 108.36 (32) Ru(~)-S-RU(~) 73.07 (7) Ru(3)-S-C(1) 107.29 (32) Ru( l)-Ru(2)-S 62.84 (5) Ru(l)-C(l)-S 91.62 (40) Ru(~)-Ru(~)-S 52.70 (5) Ru(l)-Ru( 3)-S 66.10 (6) Ru(~)-Ru(3)-S 54.22 (6)

(B)Ru-Ru-CO Angles 143.7 (3) 96.4 (3) 117.2 (3) 150.1 (3) 110.3 (3) 96.2 (3) 92.1 (3) 161.8 (3) 95.2 (3)

(C) S-C and C-C Distances within the CHzSEt Ligand S-C(l) 1.727 (10) C(2)-C(3) 1.516 (17) S-C(2) 1.834 (12)

-9.9 ppm, 214 ppm upfield from the chemical shift of the methylidyne carbon resonance of (p-H),Ru,(p,-CSEt)(CO),. This is consistent with the general trend in 13C chemical shifts: M,(p-CR) > M,(p-CR,) > MCR3.19 Description of the Crystal and Molecular Structure of ( ~ - H ) R U , ( ~ ~ - T ~ W H ~ S E ~The ) ( Ccrystal O)~ contains discrete molecular units of (p-H)Ru3(p3qZCH,SEt)(CO), that are separated by normal van der Waals' distances; there are no abnormally short intermolecular contacts. Each molecule is chiral, but the crystal contains an ordered racemic mixture by virtue of the inversion centers and n glide planes present in space group P2,/n. The atomic labeling scheme and molecular geometry are illustrated in Figure 1. Figure 2 provides a stereoscopic view of the molecule. Interatomic distances and angles are collected in Tables I11 and IV. The (p-H)Ru3(p3-$-CHZSEt)(CO)9 molecule is based upon a triangular array of ruthenium atoms. Each ruthenium atom is in a different stereochemical environment, and each is linked to three terminal carbonyl ligands (two equatorial and one axial). The p3-v2-CHZSEtligand caps the triangular ruthenium cluster with the sulfur atom bridging Ru(2) and Ru(3) (Ru(2)-S = 2.348 (2) A,Ru(3)-S = 2.302 (2) A, and Ru(2)-S-Ru(3) = 73.07 ( 7 ) O ) and with the methylene carbon atom, C(l), bonded to Ru(1) via (19) A pertinent example is the series (p-H),Os,(w,-CH!(CO),, (wH)zOs3(p-CH2)(CO),o,and ( ~ - H ) O S ~ ( ~ - $ ~ - C H ~for ) ( Cwhich O ) ~ the ~ , 13C chemical shifts are 118.4, 25.8, and -59.2 ppm, respecti~ely.~~

R u ( ~ ) - R u ( I ) - C ( I ~ ) 87.4 (3) Ru(3)-Ru(l)-C(12) 95.0 (3) Ru(3)-Ru(l)-C(13) 167.3 (3) Ru(l)-Ru(3)-C(31) 96.8 (3) Ru(l)-Ru(3)-C(32) 163.6 (3) 92.9 (3) Ru(l)-Ru(3)-C(33) Ru(2)-Ru(3)-C(31) 156.6 (3) R u ( ~ ) - R u ( ~ ) - C ( ~100.0 ~ ) (3) R u ( ~ ) - R u ( ~ ) - C ( ~ 98.3 ~ ) (3)

(C) OC-Ru-CO and Ru-C-0 Angles C(ll)-R~(l)-C(l2) 93.8 (4) RU(l)-C(ll)-O(ll) C(ll)-R~(l)-C(13) 95.9 (4) R~(l)-C(12)-0(12) C(12)-Ru(l)-C(13) 97.0 (4) R~(l)-C(13)-0(13) C(21)-Ru(2)-C(22) 96.2 (4) R~(2)-C(21)-0(21) C(21)-Ru(2)-C(23) 92.0 (4) Ru(2)-C(22)-0(22) C(22)-R~(2)-C(23) 100.6 (4) R~(2)-C(23)-0(23) C(31)-Ru(3)-C(32) 96.9 (4) Ru(3)-C(31)-0(31) C(31)-R~(3)-C(33) 96.4 (4) R~(3)-C(32)-0(32) C(32)-Ru(3)-C(33) 94.4 (4) R~(3)-C(33)-0(33) C (21)-Ru(2)-S C(22)-Ru(2)-S C(23)-Ru(2)-S C (31)-Ru(3)-S C(32)-Ru(3)-S

(D) OC-Ru-S and OC-Ru-C Angles 95.8 (3) C(33)-Ru(3)-S 110.2 (3) C(ll)-Ru(l)-C(l) 147.1 (3) C(l2)-R~(l)-C(l) 106.6 (3) C(l3)-R~(l)-C(l) 101.3 (3)

177.4 (8) 178.9 (8) 173.8 (8) 178.3 (9) 178.7 (9) 179.2 (8) 178.5 (8) 179.4 (9) 178.9 (8) 150.2 (3) 89.0 (4) 174.4 (4) 87.5 (4)

(E) Angles Involving the p3-q2-CH2SEtand p-H Ligands Ru(2)-S-C (2) 123.7 (4) Ru(l)-Ru(2)-H(12) 28.8 (21) Ru(3)-S-C (2) 125.1 (4) Ru(2)-Ru(l)-H(12) 33.9 (25) S-C(2)-C(3) 110.4 (8) Ru(l)-H(12)-Ru(2) 117 (4) Ru(3)-Ru(2)-H(12) 87.2 (21) S-Ru(2)-H(12) 82.1 (21) Ru(3)-Ru(l)-H(12) 90.7 (25) C(l)-R~(l)-H(l2) 87.6 (25) C(ll)-R~(l)-H(l2) 176.3 (25) C(21)-Ru(2)-H(12) 177.8 (22)

Ru(1)-C(l) = 2.188 (9) A. The three Ru-Ru linkages are inequivalent. That bridged by the p-SEt ligand is the shortest, with Ru(2)-Ru(3) = 2.769 (1)A;this is contracted relative to the p-hydrido-y-thioethyl-bridgedRu-Ru distance of 2.843 (1) 8, in (p-H)Ru3(C0),,(p-SEt).ld The Ru(l)-Ru(2) linkage is the longest; this equatorially hy-

810 Organometallics, Vol. 6, No. 4, 1987

Churchill et al.

drido-bridged distance is expanded to 2.974 (1) A, in Table V. Important Molecular Planes and Atomic agreement with the equatorially hydrido-bridged Ru-Ru Deviations Therefrom (A) for (p-H)Ru3(p3-q2-CH2SEt)(CO)S bond length of 2.967 (1) A in ( ~ - H ) , R U ~ ( ~ ~ - ~ ~ - C H C ( O ) (A) The Triruthenium Plane OCH3)(CO)g1fand with measurements from other equatorially hydrido-bridged M-M systems.20-22 The non0.3707X - 0.9286Y - 0.01812 + 5.4443 = 0" Ru(1)* O(W 0.673 (7) 0.000 bridged Ru(l)-Ru(3) distance is 2.818 (1)A (cf. Ru-Ru(av) Ru(2)* C(21) 0.208 (9) 0.000 = 2.854 (5) A in the parent binary carbonyl RU~(CO)~;~). Ru(3)* O(21) 0.354 (8) 0.000 The trinuclear cluster is associated with a total of 48 S C(22) 0.505 (10) 1.827 (2) outer valence electrons. (Using the neutral atom/neutral O(22) 0.790 (9) H(12) -0.14 (6) ligand electron-counting formalism, we get 24 electrons C(23) -1.906 (10) C(1) 2.139 (8) from the three d8 Ru(0) atoms, 18 electrons from the nine O(23) -3.032 (7) C(2) 3.359 (12) C(3) C(31) 0.477 (8) 4.181 (14) terminal carbonyl ligands, 5 electrons from the p3-q2O(31) 0.760 (7) C(11) 0.262 (8) CHzSEt ligand, and 1electron from the p-hydride ligand.) (332) 0.171 (11) O(11) 0.452 (6) Electron counts at the individual metal centers are inC(l2) OW) 0.269 (9) -1.914 (9) equivalent with 18 electrons a t Ru(3), 171/2electrons at C(33) -1.870 (9) O(12) -3.033 (7) Ru(l), and B1/, electrons at Ru(2). O(33) -3.003 (6) C(13) 0.392 (9) If we ignore the direct Ru(l)-Ru(2) i n t e r a ~ t i o nthen ,~~ (B) The Ru(2)-S-Ru(3) Plane each ruthenium atom is seen to have an approximately 0.6545X - 0.0228Y - 0.75572 + 5.0209 = 0" octahedral coordination environment. The R u ( C O ) ~ Ru(2)* 0.000 C(1) 1.596 (10) groups are associated with OC-Ru-CO angles of 92.0 Ru(3)* 0.000 H ( W 1.85 (7) (4)-100.6 (4)O, the p-hydride ligand lies in a position trans S* 0.000 C(2) -1.305 (12) to two carbonyl ligands (C(ll)-Ru(l)-H(l2) = 176.3 (25)' Ru(1) 2.484 (1) C(3) -1.212 (12) and C(Zl)-Ru(Z)-H(12) = 177.8 (22)'), the methylene (C) The Ru(2)-H(12)-Ru(l) Plane carbon is trans to a carbonyl group (C(l)-Ru(l)-C(l2) = -0.2276X + 0.9738Y - 0.00232 - 5.8967 = 0" 177.4 (4)O), and the sulfur atom is in a distorted trans Ru(l)* 0.000 -2.090 (8) configuration relative to two other carbonyl ligands (C0.000 S -1.653 (2) Ru(2)* (23)-Ru(2)-S = 147.1 (3)O and C(33)-Ru(3)-S = 150.2 0.000 C(2) -3.090 (12) H(12)* (3)O). Ru(3) 0.357 (1) C(3) -3.763 (14) The p-hydride ligand was located with limited precision (D) Dihedral Angles (Ru(l)-H(12) = 1.61 (7) A, Ru(2)-H(12) = 1.87 (7) A, and plane A/B 101.99' (78.01O) Ru(l)-H(12)-Ru(2) = 117 (4)O) but appears to be close to plane AJC 171.32' (8.68') coplanar with the triruthenium plane. (The deviation from 82.62' (97.38') plane B JC the Ru3 plane is -0.14 (6) A, and the dihedral angle bea Orthonormal coordinates. Only atoms marked with an astertween Ru(l)-Ru(B)-Ru(3) and Ru(l)-H(12)-Ru(2) planes isk were used in calculating the plane. is 171.3O-see Table V.) The P,--,~~-CH,SE~ ligand appears to incorporate a norbeen prepared. Reactions of Co3(p3-CBr)(C0),with armal Ru-C CT bond (Ru(l)-C(l) = 2.188 (4) 8, as compared enethiols and triethylamine or with M~,&I(SR)~ were used to a predicted Ru-C distance of approximately 2.20 8, to prepare a number of examples of the type co3(&based upon r(C(sp3)) = 0.77 A and r(Ru) = 1.43 A from CSR)(C0)9.16,26 The mixed-metal analogue Cp2Fe2Co'/&Ru-Ru) in RU,(CO)~~). The sulfur atom has a distorted ( K ~ - C S M ~ ) ( Cwas O ) synthesized ~ via the reaction of [Co(chiral) tetrahedral environment in which the S-C(l) (CO),-] with [Cp,Fe,(p-CSMe)(p-CO)(CO),+], prepared by distance of 1.727 (10) A is significantly shorter than the methylation of the corresponding t h i ~ c a r b o n y l . ~It~ is normal S-C(2) distance of 1.834 (12) A (cf. the accepted worthy of note that the CSMe ligand of Cp2Fe2Co(p3C-S distance of 1.817 f 0.005 A in paraffinic and saturated CSMe)(CO), is bound through carbon to all three metals heterocyclic thio corn pound^^^). and also through sulfur to the cobalt. The most likely The Ru-CO bond lengths range from 1.884 (9) through explanation for the ability of the CSR ligand to bond in 1.944 (10) A. Although there is little variation in these an v2 fashion is the strength of the M-S bond. distances, the longest are trans to Ru-Ru bonds (Ru(2)The synthesis of (p-H)3R~3(p3-CSEt)(C0)9 was derived C(22) = 1.944 (10) and Ru(l)-C(13) = 1.941 (9) A) and the from earlier work by Seyferth and co-workers (in which shortest is trans to the p-hydride ligand (Ru(l)-C(ll) = base-catalyzed attack by thiols on Co3(p3-CBr)(CO), af1.884 (9) A). There is no clear difference between axial forded the analogous Co,(p,-CSR)(CO), clusters)16 and and equatorial Ru-CO distances. from our previous synthesis of (p-H),Ru3(p3-COEt)(CO), Finally, we note that C-0 distances range only from by reaction of (p-H),Ru3(p3-CBr)(C0), with sodium eth1.120 (12) through 1.157 (11) 8, and that all Ru-C-0 oxide/ethanol.lO As noted by Seyferth, these reactions are systems are close to linear (173.8 (8)' 179.4 (9)'). unlikely to involve direct attack of the nucleophile on the alkylidyne carbon. Substitution of alkoxide for bromide Discussion in alcohol solution may involve an SN1-typemechanism; Halide Displacement from ( P - H ) ~ R u ~ ( ~ ~ - C B ~ ) ( C Oremoval ),. of bromide with AlC13 in unreactive solvents forms Few clusters containing the CSR ligand have previously [ (p-H)3R~3(p3-CCO)(C0)9+], and treatment of (1H)3R~3(p3-CBr)(C0)9 with A1C13/benzene generates ( p (20) Churchill, M. R.; DeBoer, B. G.; Rotella, F. J. Inorg. Chem. 1976, H)3R~3(p3-CPh) (CO),, both reactions presumably involving 15, 1843. the intermediacy of [ H , R U ~ ( C ) ( C O ) ~However, ~ ] . ~ ~ this (21) (a) Churchill, M. R.; DeBoer, B. G. Inorg. Chem. 1977, 16, 878. is unlikely to be the case for replacement of bromide by (b) Churchill, M. R.; DeBoer, B. G. Inorg. Chem. 1977, 16, 2397. (22) (a) Churchill, M. R. Adu. Chem. Ser. 1978, No. 167,36. (b) Teller, thiolates in nonpolar solvents such as cyclohexane. Sey-

-

R. G.; Bau, R. Struct. Bonding (Berlin) 1981,44, 1. (23) Churchill, M. R.; Hollander, F. J. Hutchinson, J. P. Inorg. Chem. 1977, 16, 2655. (24) Kampe, C. E.; Boag, N. M.; Knobler, C. B.; Kaesz, H. D. Inorg. Chem. 1984,23, 1390. (25) Spec. Publ.-Chem. SOC.1965, No. 18, p S22s.

( 2 6 ) Seyferth, D.; Merola, J. S.; Berry, D. H. Z. Anorg. Allg. Chem. 1979, 458,-267. ~~

(27) Schroeder, N. C.; Richardfion, J. W., Jr.; Wang, S.-L.; Jacobson, R. A,; Angelici, R. J. Organometallics 1985, 4, 1226.

Structure of (p-H)Ru3(r3-712CH2SEt)(CO),

Organometallics, Vol. 6, No. 4, 1987 811

ferth and co-workers have proposed a radical chain mechanism of the SRNltype. We believe that this mechanism, shown in Scheme I, is also appropriate for the ruthenium analogues. In support of this mechanism: (1)the yields are higher in nonpolar solvents, but the reaction does require the presence of triethylamine, (2) the yields are quite variable under apparently identical conditions, suggesting the presence of radical intermediates, and (3) treatment of (p-H),Ru3(p3-CBr)(C0), with triethylamine/phenol in dichloromethane yields only ( P - H ) ~ R U ~ (p3-CH)(C0),, not (p-H)3R~3(p3-COPh)(CO)g, suggesting the intermediacy of the [H3Ru3(C)(CO),*]radical.28 Further experiments designed to probe the mechanism of this reaction are in progress. Scheme I H3Ru3(CBr)(C0),+ SEt[H3Ru3(CBr)(CO),*-] SEt'

-

[H3Ru3(CBr)(CO),'-]

-+

[ H ~ R u ~ ( C ) ( C O+ ) ~SEt*]

X I

X

\

s-..

' 2 -

' I

\

+

[H3R~3(C)(C0)9*] + Br-+

-

[H3Ru,(CSEt)(CO)g'-]

H,Ru,(CSEt)(CO),'- + H,Ru3(CBr)(C0), H3Ru3(CSEt)(C0),+ H,RU~(CB~)(CO)~'Reductive Elimination of CH3X from Trimetallic Clusters. An Analogy to Metal Surface Chemistry? Relatively few alkyl-containingclusters have been prepared previously. Some examples include HOs3(CH2C02Et)(CO)10,29 H O S ~ ( C H M ~ C O ~ E ~ ) HOs3(CH(C02Et)(CO)~~,~ CH2C02Et)(C0)10,29 HOs3(CHMeOMe)(CO)10,30HOs3(CHMeSPh)(CO)lo,31H O S ~ ( C H ~ ) ( C OHOs3(CH2C)~~,~~ H3)(C0)10,33 Os3(CH3)(I)(CO)lo,34 and HOs3(NCO)(succinoyl) (C0)1,,.35 Several examples are stabilized by coordination of a substituent group on the alkyl chain (in some cases an agostic hydrogen) that acts as a two-electron donor, but all containing hydride ligands are unstable with respect to reductive elimination and those with p-hydrogens unstable to alkene elimination in the presence of donor ligands. None of these have been formed by reductive elimination reactions. To our knowledge there are no previous reports of Ru analogues, although alkyl intermediates must be important in the formation of Ru3(X)(OCEt)(CO),, (X = C1, Br, or I) and HRu,(OCEt)(CO),, from HRu,(X)(CO),, and HRu3(CO),,-, respectively,%and in alkene hydroformylation and hydrogenation catalyzed by Ru cluster^.^,^^ The rearrangement of (p-H),Ru,(p3-CSEt)(CO), to (pH)Ru3(p3:q2-CH2SEt) (CO), involves the migration of two hydride ligands to the methylidyne carbon and coordination of the sulfur atom to the two unsaturated metal atoms thus formed. The strength of the Ru-S bonds makes (28) Bower, D. K.; Keister, J. B., unpublished results. (29) Keister, J. B.; Shapley, J. R. J . Am. Chem. SOC. 1976, 98, 1056. (30) Boyar, E.; Deeming, A. J.; Arce, A. J.; De Sanctis, Y. J. Organomet. Chem. 1984,276, C45. (31) Boyar, E.; Deeming, A. J.; Henrick, K.; McPartlin, M.; Scott, A. J. Chem. SOC.,Dalton Trans. 1986, 1431. (32) Calvert, R. B.; Shapley, J. R. J. Am. Chem. SOC. 1977, 99, 5225; 1978,100,6544. (33) Cree-Uchiyama, M.; Shapley, J. R.; St. George, G. M. J . Am. Chem. SOC.1986,108, 1316. (34) Morrison, E. D.; Bassner, S. L.; Geoffroy, G . L. Organometallics 1986,5, 408. (35) Zuffa, J. L.; Gladfelter, W. L. J.Am. Chem. SOC.1986,108,4669. (36) Kampe, C. E.; Boag, N. M.; Kaesz, H. D. J. Am. Chem. SOC.1983, 105, 2896. (37) For representative examples, see: (a) Suss-Fink, G. J. Organomet. Chem. 1980,193, C20. (b) Braca, G.; Sbrana, G. Chim. Ind. (Milan) 1974, 56, 110. (c) Zuffa, J. L.; Blohm, M. L.; Gladfelter, W. L. J.Am. Chem. SOC.1986, 108, 552. (d) Doi, Y.; Koshizuka, K.; Keii, T. Inorg. Chem. 1982,21, 2732. (e) Suss-Fink, G.; Herrmann, G. J . Chem. SOC.,Chem. Commun. 1985, 735.

/ \ '

1.

H

L

\ S -Ru-/-R~ \' /

/

co

F'

H ;.

R u ~ ( C O ) , ~t C H 3 X

\

\H-R,,/

'I

'

Proposed mechanism for isomerization of H ) ~ R u ~ ( ~ ~ - C S E to ~ )(FL-H)RUB(FL3-~'-CH2SEt)(C0)9. (CO)~ Figure 3.

(p-

possible the isolation of the alkyl-containing cluster even under an atmosphere of carbon monoxide. Cleavage of a single Ru-S bond and the addition of carbon monoxide presumably should form H R u , ( ~ - ~ ~ - C H ~ S E ~ ) ( C O ) , , , analogous to HOs3(CHMeSPh)(C0)1,,.31 Thermolysis of other clusters (p-H)3R~3(p3-CX)(C0)9 (X = Ph, C1, or C02Me)or of GL-H)2R~3(p3-~2-CHC02CH3)(CO)g under CO forms the appropriate alkane and R U , ( C O ) ~ ~ . ~ The mechanism of rearrangement of ( P - H ) ~ R U ~ ( ~ ~ CSEt)(CO), to (p-H)Ru3(p3-$-CH2SEt)(C0),is of interest with respect to the mechanism of cleavage of CH3X from GL-H)3R~3GL3-CX)(C0)9 (X = Ph, C1, or C02Me)under CO. We have proposed that the mechanism of reductive cleavage involves a preequilibrium between the ground state and a tautomer containing an agostic Ru-H-CX bond, with the rate-determining step being cleavage of the Ru-H-CX bond to form an unsaturated intermediate (Figure 3L8 It may be significant that the free energies of activation for rearrangement of (p-H),Ru3(p3CC02Me)(C0),to GL-H)2R~3(p3-t12-CHC02CH3)(C0)9 (AG* = 112 kJ/mol (26.7 kcal/mol) at 70 "C)lf and for rearrangement of ( P - H ) ~ R U ~ ( ~ ~ -(CO), C S Eto ~ )(p-H)Ru3(p3.r12-CH2SEt)(CO),(AG*= 108 kJ/mol (25.9 kcal/mol) at 70 "C), both reactions forming products in which the methylidyne substituent ends up coordinated to the cluster, are much lower than the free energies of activation for reductive elimination of CH3X from ( P - H ) ~ R U ~ ( ~ ~ CX)(CO), (X = Ph or C1; AG* = 129 and 123 kJ/mol, respectively) where X cannot act as a ligand.8 This suggests that when X has Lewis base character, it may participate directly in the reductive elimination process by stabilization of the incipient site of unsaturation (Figure 3).

Churchill et al.

812 Organometallics, Vol. 6, No. 4, 1987

termining step in the reaction of CO with hydrogen to form methane (Scheme 11). Sequential hydrogenation of surface carbide is the proposed mechanism. On the basis of inverse isotope effects for methanation on alumina- and silicasupported Ru, the rate-determining step was proposed to be one of the steps in which a C-H bond is formed,39and the inverse isotope effect for methanation on Ni was interpreted to indicate partial CO hydrogenation prior to C-0 bond d i s s o ~ i a t i o n . ~On ~ the other hand, a SIMS HOs3(HCH2)(CO)io+ H20~3(CHz)(CO)io (1) study of methanation on Ni(ll1) identified surface-bound methylidyne, methylene, and methyl intermediates, all H3Fe3(CH)(CO),+ H,Fe,(HCH)(CO), (2) having similar (within an order of magnitude) surface H,Fe,(HCH)(CO), + HFe3(H2CH)(CO), (3) concentrations,4' and the rate of desorption of methane by combination of methyl and hydrogen atoms on the Our observation that a single hydride migration occurs Ni(ll1) surface has been determined to be lo6times faster upon pyrolysis of (p-H)3R~3(p3-CCOzMe)(CO)g, forming than the rate of CO h ~ d r o g e n a t i o n ,thus ~ ~ indicating (p-H)2R~3(p3-v2-CHC02CH3)(C0)9,1f suggests that the two rate-determining C-0 bond cleavage. However, the relahydride migrations required to form (p-H)Ru3(p3-q2tive rates of the successive C-H bond-forming steps have CH,SEt)(CO), occur sequentially through the intermediacy not been determined. of (p-H)2R~3(p3-v2-CHSEt)(C0)9 that should have a Scheme I1 structure analogous t o that of (p-H),Ru3(p3-q2CHC02CH3)(CO),. Since we see no evidence for an inCO C(ads) + O(ads) termediate in the formation of (p-H)Ru3(p3-v2-CH,SEt)C(ads) + H(ads) CH(ads) (CO),, this suggests that the second reductive elimination CH(ads) + H(ads) CH,(ads) is faster than the first. Increasing rates for successive C-H eliminations are CH2(ads)+ H(ads) CH3(ads) suggested by other evidence as well. We have previously + H(ads) CH,(g) CH,(ads) noted that for (p-H)3R~3(p3-CX)(C0)9 the Ru-CX bond length increases in the order X = C1< Me < p-tolyl, the These trimetallic cluster models may provide informasame as the trend of decreasing H-CH2X bond strength, tion concerning the structures of the surface-bound inand have thus proposed that the Ru-CX bond strength termediates, the mechanism of the desorption process, and parallels that of the corresponding H-CH2X bond. A the relative rates of the individual steps. Investigations structural comparison of (p-H),Ru3(p3-CX)(C0),(X = C1,% of the mechanisms of reductive elimination from these Me,Sbor p-tolylie),(p-H)2R~3(p3-q2-CHC02CH3)(CO)g,1f and clusters are in progress. ( ~ - H ) R u ~ ( ~ ~ - ~ ~ - Cshows H ~ S Ethat ~ )there ( C Ois)an ~ inAcknowledgment. This work was supported by the crease in the Ru-C bond length upon successive C-H National Science Foundation through Grant CHE85-20276 eliminations. Thus, the average Ru-C bond length into J. B. K. creases from (p-H)3R~3(p3-CX)(C0)9 (average = 2.088 A) to (p-H)zR~3(p3-v2-CHC02CH3)(C0)9 (average = 2.140 A) Registry No. (p-H)3R~3(p3-CBr)(CO)g, 73746-95-9; (pH ) ~ R u ~ ( ~ ~ - C S E ~ ) 100852-22-0; (CO)~, (~L-H)RU~(~~-~'-CH~SE~)to (p-H)Ru3(p3-v2-CH2SEt)(C0), (2.188 A). This suggests (CO)9, 100852-23-1; ethanethiol, 75-08-1. that the Ru-C bond strength may decrease in the order Ru-p3-CX > Ru-p2-CHX > Ru-CH2X. Another indicaSupplementary Material Available: A table of anisotropic tion of the increasing facility of successive reductive elimthermal parameters (1 page); a listing of observed and calculated inations is the qualitative order of increasing ease of destructure factor amplitudes (13 pages). Ordering information is composition of an analogous Os cluster series under CO: given on any current masthead page. (P-H)~OS~(P~-CH) (C0)g < ( I ~ - H ) ~ O S , ( ~ ~ - C H ~